Alkaline earth sulfonates



Patented Mar. 7, 1950 EARTH SULFQNATES Milton P. ,Kleinhoiz, East Chicagmlndi, assignor to Sinclair Refining Company, New York, N- Y a corporation of Maine No Drawing. Application September 16, 1947, Serial No. 774,428

3- Claims.

My invention resides in a process for producing compounds of the formula (RCOCHLSO3) 2M where R represents an alkaryl radical comprising an alkyl group of from about 10 to about 26 carbon atoms and M represents an alkaline earth metahpreferably calcium or barium.

Such compounds may be considered. and named as derivatives of acetophenone. They are surface-active and are generally useful as wetting, cleansing and dispersing agents. As exemplary of the compounds may be mentioned the alphacalcium and barium sulfonates of laurylacetophenone, tetradecylacetophenone, hexadecylac et ophenone, heptadecylacetophenone, octadecylacetophenone, docosanylacetophenone, and the like.

Unlike presently commercially available synthetic sulfonates of related chemical structure, the compounds are soluble to a more than appreciable extent in mineral oils. It is my belief that this oil solubility obtains by reason of the sulfo group being positioned alpha with reference to the carbonyl group which allows of chelation be tween the metal and the carbonyl oxygen, but, of course, I am not to be held for the accuracy of this hypothesis. The oil solubility of the compounds is such as to permit of their use as addends in lubricating oils to which they impart a detergent property. 7

accordance with the process of the invention the compounds are produced metathetically by reacting alkaline earth metal salts of mineral acids with compounds of the formula where R has the same significance as above and M represents an alkali metal. The reaction will be readily understood from the following equations:

I have found that the reaction proceeds'to best advantage when carried out in the presence of polar solvent, most suitably Water, or a Wateralcohol mixture, a 59:50 mixture of iso-propanol and water. for example, using slightly more than. theoretically required amount of the alkaline rth metal salt. The temperature may vary within the range 119 F, to 210F.

The alkali metal -containing sulfo-comp'ounds employed in my process are readily produced by the process described and claimed in my copending' application, .Serial No. 774,427, filed September 16, 1947, by reacting alkylated aromatic hydrocarbons having long alkyl side chains first with chloracetyl chloride and then with alkali metal sulphite. as the starting material either single hydrocarbons or mixtures. .Also, I may use, as the starting material, a petroleum oil fraction predominating in or containing'substantial proportions of hydrocarbons of the' requisite structure, the product. in such case being an oil concentrate containing a plurality of compounds conforming to the-type formula immediately above. "This concentrate or oil-free mixtures of the alkali metalsulfo-compounds maybe employed in lieu of single compounds in the practice of my present process' Using the concentr te the product obtained represents an oil concentrate of compou' conforming to the type formula first appearing herein.

The detailed practice of the process will be readily understood from the following examples which are not to be taken as in any way limitative of the scope of the invention.

Example I This example illustrates the preparation of an oil concentrate ofsodium sulfo-acetylated compounds suitable for use in the preparation of a concentrate of compounds of-the invention.-

The laboratory tests on the oil used were as follows:

Gravity 26.9 Flash 455 Fire 53o Vis. 100 434 Vis. 210 57.3

Pour 1 1, .10 Color 3 /2-I- Carbon residue .03 Acid No 0.0 Molecular Weight (approximate) 1 410 The equipment included a 3-liter, 3-neck flask, mercury seal stirrer, dropping funnel, reflux condenser, and a drying tube.

312 grams (2.34 moles) anhydrous aluminum chloride was mixed in the reaction flask with 1000 c. ,c. isopentane. 2460 grams (6 moles) of the oil was mixed with 177 grams (1.56 moles) of chloracetylchloride. The "mixture of oil "and ciiloracetyl chloride was'added dropwi'se to the In practicing this process I may use aluminum chloride over about one and one-half hours with mixing. The reaction started at room temperature but proceeded with refluxing of the isopentane. After two hours additional stirring, the mixture was poured into one and a half liters of ice and water with stirring. 500 c. c. of ether was added and. the mixing continued two hours. The organic phase was separated, washed with cold dilute hydrochloric acid, followed by a water wash, a cold dilute sodium carbonate wash, and a final water wash. The oil layer was filtered and the solvent was removed by topping finally under vacuum over a steam bath. The topped oil contained 1.8% chlorine, a yield of 84% of chloracetyl-ated aromatics.

1,545 grams of the solution prepared as just described, containing 0.78 mole of chloracetylated aromatics, was charged to a one gallon autoclave. 3'78 grams (3 moles) anhydrous sodium sulfite in 1,500 0.0. water and 750 c. c. denatured alcohol representing a mixture of 95% ethanol and methanol in the proportions of :1 by volume were added and the mixture reacted at 300 F.:10 F. for hours with stirring. At the termination of the reaction, the water layer was found to contain um'eacted sodium sulfite and sodium chloride. The dehydrated and filtered oil (1,220 grams) contained 0.97% sodium, 1.09% sulfur, and 0.43% chlorine. Conversion of chlorine in the chloracetylated aromatic molecules to the sodium sulfonate was 86%.

Example II 300 grams of the sodium sulfo-acetylated oil from Example I, containing 2.92 grams sodium,

was mixed with 8.33 grams calcium chloride (103% of the theoretical amount) in a water. solution (34 c. 0. 1120) for 2 hours at 160 F. 2.63, grams calcium chloride (about of the theoretical amount) in 20% water solution (10.5

c. c. H2O) was then added and the mixing continued an additional 2 hours at 160 F. The oil was dehydrated by heating to 280 F. and filtered. The filtrate contained 0.91% calcium; 0.07% sodium, 0.72% chlorine, and 1.24% sulfur.

Example III 6132 grams of sodium sulfo-acetylated oil, containing 46.16 grams sodium, was reacted with 128 grams calcium chloride (115% theoretical amount) in 425 c. c. of water. The oil was heated with mixing to 220 F. for two hours, after which time the mixture was allowed to settle and the calcium chloride solution drawn off. The process was repeated three times. The oil was Washed with '70 volume H20 and allowed to settle. The oil layer was dehydrated by heating to 280 F. and filtered. The filtrate (5200 grams) contained 0.48% calcium, 0.02% sodium, 0.37% chlorine, 0.89% sulfur, and had an acid number of 1.68. The filtrate was neutralized with 188 grams of calcium hydroxide with 5% water added (270 c. c. H20) and the mixture stirred 2 hours. Dehydration was accomplished by heating to 280 F. The analysis of the dry, filtered oil showed 0.73% calcium, 0.02% sodium, 0.18% chlorine, and a 1.6 (basic) neutralization number.

Example IV Gravity Flash of the I grams of calcium chloride in a 20% 4 Fire 635 Vis. 1752 Vis. 210 126.9 V. I 96 Pour 5 Color 6+ Carbon residue 0.36 Acid No 1- 0.0

250 grams of the sodium sulfo-acetylated oil, containing 0.04 mole of sodium sullo-acetylated aromatics, was heated to 180 F. and 5.63 grams of theoretical) of barium chloride in 200 c. c. of a 50:50 blend of isopropanol and water was added. The mixture was stirred and heated to 195 F. It was then allowed to settle at F. for three hours and to cool overnight. The alcohol-water layer was removed and a second treat made with 115% of theoretical barium chloride solution. The mixture was heated to 195 F. and allowed to stand overnight at 170 F. The alcohol-water layer was removed, 225 c. c. of water added and the mixture stirred and heated to 210 F. and allowed to settle at 210 F. overnight. The emulsion formed had not broken, so the mixture was transferred to a separatory funnel and heated with a steam finger until separation was complete. The oil layer was heated to 300 F. for 30 minutes and filtered hot. The product contained 1.43% barium (1.1% theoretical), 0.01% sodium, 0.15% chlorine, and 0.56% sulfur.

Example V Example VI 458 grams (1.45 moles based on the sodium content) of alpha-sodium sulfonate of p-laurylacetophenone was dissolved in one liter of xylene and the solution heated to F. 92.2 grams of calcium chloride (115% of theoretical) in a 20% aqueous solution was added dropwise to the xylene solution, the temperature dropping to 170 F. The mixture was stirred at 170 F. for 2 hours before being allowed to settle overnight.

The aqueous layer was drawn off and 92.2 aqueous solution was added to the xylene layer at room temperature following which the mixture was heated, with stirring. to 220 F. in 2 hours. It was necessary to add more xylene from time to time as the mixture emulsified and became rather viscous. The emulsion was broken by heat and the water drawn oil.

The xylene solution was heated to 150 F., 108 grams of calcium hydroxide and 75 cc. of water added, and the mixture stirred at 150-180 F. for 2 hours. It was then heated to 280 F. and held at that temperature for 15 minutes before it was filtered and topped under plant vacuiun to 330 F. bottom temperature. A yield of 396 grams of product was obtained. The product, consisting chiefly of the desired alpha-calcium sulfonate of p-laurylacetophenone, contained 5.28% calcium, 5.38% sulfur, 0.68% chlorine, 0.08% sodium, and had an acid number of 9.5.

I claim: 1. In" a process for preparing a compound of the formula (RCOCH2SO3) 2M where R represents an alkaryl radical comprising an alkyl group of from about to about 26 carbon atoms, and M represents an alkaline earth metal, the step which consists of reacting a water soluble alkaline earth metal chloride with a compound of the formula M represents an alkali metal, by mixing the alkali metal compound with an excess of the chloride in the presence of a polar solvent at a tem perature within the range of 110-220 F.

2. In a process for producing an oil concentrate of compounds of the formula where R represents an alkaryl radical comprising an alkyl group of from about 10 to about 26 carbon atoms, and M represents an alkaline earth metal, the step which consists of reacting a water soluble alkaline earth metal chloride with an oil concentrate of compounds of the formula REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,416,818 Carter Mar' 4, 1947 FOREIGN PATENTS Number Country Date 463,544 Great Britain Mar. 30, 1937 

1. IN A PROCESS FOR PREPARING A COMPOUND OF THE FORMULA 